Patent GB-931491-A (GB)
Title: Phosphorus-containing lubricating oil additives and processes for the manufacture thereof
Inventor: SABOL ALBERT R
IPC: C07F9/04
Filed: 1959-08-12
Abstract: In the production of a lubricating oil additive comprising the neutralized reaction product of a phosphorus sulphide and a normally nongaseous hydrocarbon, e.g. a mono-olefin hydrocarbon polymer, the reaction mixture after neutralization of the phosphorus sulphidehydrocarbon reaction product with a basic alkaline earth metal compound is heated with formic acid prior to the separation of the liquid product from the solids present in the neutralized reaction mixture.  The process is preferably carried out by reacting the hydrocarbon with from 1,0 to 50% by weight of a phosphorus sulphide, e.g. P2S5, at 200 DEG  to 600 DEG F., hydrolysing the reaction product, e.g. with steam, usually at 200 DEG  to 600 DEG F., whereby inorganic acids of phosphorus are formed, contacting the hydrolysis products with an adsorbent to adsorb inorganic acids, separating the adsorbent from the adsorbent treated product, neutralizing the latter with from 4 to 15 parts by weight of a basic alkaline earth metal compound, e.g. barium oxide or hydroxide, per part by weight of the phosphorus present in the adsorbenttreated product, the neutralization being carried out in the presence of a C1-C3 aliphatic alcohol, heating the neutralization products and vaporizing at least a substantial portion of the alcohol therefrom, adding formic acid in an amount of 0, to 50% by weight based on the neutralization product from which alcohol has been vaporized, heating the resultant mixture to 200 DEG  to 500 DEG F. and filtering at this temperature to remove solids therefrom.  The hydrocarbon used is preferably a mono-olefin polymer resulting from the polymerization of a mono-olefin having less than 6 carbon atoms, or a mixture of monoolefin and isomono-olefin polymers, said polymers having molecular weight of from 150 to 50,000 or more and preferably from 500 to about 10,000 suitable polymers being obtainable by liquid phase polymerization of a hydrocarbon mixture containing mono- and isomonoolefins, e.g. butylene and isobutylene at about -80 DEG  to about 100 DEG F. in the presence of a metal halide catalyst of the Friedel-Crafts type, e.g. boron fluoride or aluminium chloride.  A hydrocarbon mixture containing isobutylene, butylenes and butanes recovered from petroleum gases produced in the cracking of petroleum oils is particularly suitable for preparing the polymers.  The phospho-sulphurization is preferably effected in a non-oxidizing atmosphere, e.g. nitrogen.  Suitable adsorbents for treating the hydrolysis products include various clays, fuller's earth, bentonite, magnesite and bauxite and the basic alkaline earth compound used in the neutralization should preferably be used in an amount sufficient to yield a product having excess basicity, e.g. one having a weight ratio of barium to phosphorus of up to about 8:1. The adsorbent treated product is preferably diluted with a normally liquid hydrocarbon before the neutralization step and some water may also be present in addition to the C1-C3 alcohol during this step.  The basic alkaline earth compound may be barium oxide or hydroxide or a carbonate or sulphide, e.g. of calcium, may be used and the neutralization is preferably effected under reflux conditions.  An example is given in which the hydrocarbon is a butylene polymer having a molecular weight of about 850, the phosphorus sulphide is P2S5, and the alkaline earth metal compound is barium oxide.  The product may be used in mineral lubricating oils or synthetic lubricating oils which may be of the poly-alkylene oxide or complex ester type.ALSO:In the production of a lubricating oil additive comprising the neutralised reaction product of a phosphorus sulphide and a normally non-gaseous hydrocarbon the reaction mixture after neutralisation of the phosphorus sulphide-hydrocarbon reaction product with a basic alkaline earth metal compound is heated with formic acid prior to the separation of the liquid product from the solids present in the neutralised reaction mixture.  The process is preferably carried out by reacting the hydrocarbon with from 1.0 to 50% by weight of a phosphorus sulphide, e.g. P2S5, at from 200 to 600 DEG F., hydrolysing the reaction product, e.g. with steam, usually at 200 DEG  to 600 DEG F., whereby inorganic acids of phosphorus are formed, contacting the hydrolysis products with an adsorbent to adsorb inorganic acids, separating the adsorbent from the adsorbent-treated product, neutralising the latter with from 4 to 15 parts by weight of a basic alkaline earth metal compound, e.g. barium oxide or barium hydroxide, per part by weight of the phosphorus present in the adsorbent-treated product, the neutralisation being carried out in the presence of a C1-C3 aliphatic alcohol, heating the neutralisation products, vaporising at least a substantial portion of the alcohol therefrom, admixing formic acid with the neutralisation products from which alcohol has been vaporised, the formic acid being added in an amount of 0.1 to 50% by weight based on the neutralisation products from which alcohol has been vaporised, heating the resultant mixture to 200 DEG F. to 500 DEG F. and filtering at this temperature to remove solids therefrom.  The hydrocarbon used in the process is preferably a monoolefin hydrocarbon polymer (see Group IV(a)) but other hydrocarbons may be used, e.g. paraffinic hydrocarbons such as bright stock residiums, lubricating oil distillates and waxes; olefines having 16 to 30 carbon atoms, aromatic hydrocarbons such as benzene, naphthalene, diphenyl, and alkylated aromatic hydrocarbons, e.g. benzene having alkyl substituents containing at least 8 carbon atoms.  The phosphosulphurisation is preferably effected in a non-oxidising atmosphere, e.g. nitrogen.  Suitable adsorbents for treating the hydrolysis products include various clays, fullers earth, bentonite, magnesite and bauxite.  The basic alkaline earth metal compound should preferably be used in sufficient amount to yield a product having excess basicity, e.g. one having a weight ratio of barium to phosphorus of up to about 8:1. The adsorbent treated product is preferably diluted with a normally liquid hydrocarbon before the neutralisation step and some water may be present in addition to the C1-C3 alcohol during the neutralisation step.  The basic alkaline earth metal compound may be barium oxide or hydroxide or a carbonate or sulphide, e.g. of calcium may be used.  The neutralisation is preferably effected under reflux conditions and the neutralisation product, after removing a substantial proportion of the alcohol and water (if present), is preferably heated with formic acid to about 200 DEG  to 500 DEG F. for about 2 to 3 hours and the subsequent filtration step is preferably carried out at from 300 to 350 DEG F. preferably with a filter aid.  The products may be used in mineral lubricating oils or in synthetic lubricating oils which may be of the poly-alkylene oxide or complex ester type.